CN105680040B - A kind of antimony base lithium storage materials and preparation method thereof - Google Patents
A kind of antimony base lithium storage materials and preparation method thereof Download PDFInfo
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- CN105680040B CN105680040B CN201610018437.7A CN201610018437A CN105680040B CN 105680040 B CN105680040 B CN 105680040B CN 201610018437 A CN201610018437 A CN 201610018437A CN 105680040 B CN105680040 B CN 105680040B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of antimony base lithium storage materials and preparation method thereof.The antimony base lithium storage materials are a kind of sulfantimonide of lithium, molecular formula Li3+3xSb1‑xS3, Sb is positive trivalent in formula, x=0.05 to 0.95.The preparation method of antimony base lithium storage materials is to obtain through hydrometallurgical technology and liquid-phase chemical reaction using natural stibnite mineral dust as raw material, significantly reduce environmental pollution and energy consumption.Li3+ 3xSb1‑xFor S3 when being used as lithium ion battery electrode material, its whole component in charge and discharge process, including Li, Sb and S all have electro-chemical activity, so that it be made to have very high charge/discharge capacity.Li3+3xSb1‑xS3 capacity, in terms of performance be all substantially better than existing li-ion electrode materials, have very high cost performance.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of antimony base lithium storage materials and preparation method thereof.
Background technique
Lithium storage materials are the important components of lithium battery.The lithium storage materials being commercialized at present are mainly the oxygen-containing of lithium
Hydrochlorate, such as phosphate, manganate, cobaltatess, aluminate, titanate, their common feature is: electro-chemical activity only shows
In activity lithium ion part, and lithium ion proportion in molecular weight is less, this is that such material energy densities are not high
Main cause.On the other hand, the lithium storage materials energy density based on sulfide reported at present is improved largely, and such as vulcanizes
Lithium, but their molecular structure stabilized is not so good as oxysalt, therefore charge discharge life is not good enough.
Present invention trial provides a kind of energy density height, and the service life is long, the reasonable lithium storage materials of cost performance.
Summary of the invention
Present invention aim to address problems of the prior art, and provide a kind of antimony base lithium storage materials and its preparation
Method.
A kind of antimony base lithium storage materials, it is a kind of sulfantimonide of lithium, molecular formula Li3+3xSb1-xS3, Sb is positive three in formula
Valence, x=0.05 to 0.95.
A kind of preparation method of such as antimony base lithium storage materials, its steps are as follows:
1) broken, ground stibnite powder and ammonium sulfide are mixed by the stoichiometric ratio of (1) formula, then plus are equivalent to
The water of 5 to 10 times of stibnite weight, stirring are dissolved substantially to stibnite；
Sb2S3+3(NH4)2S=2 (NH4)3SbS3 (1)
2) it is centrifuged or is separated by filtration solid-liquid two-phase, obtain (NH4)3SbS3Solution；
3) stoichiometric ratio for pressing (2) formula, in (NH4)3SbS3LiOH is added in solution, stirring is completely dissolved up to LiOH,
Obtain Li3+3xSb1-xS3Solution；
(1-x)(NH4)3SbS3+ (3+3x) LiOH=Li3+3xSb1-xS3+(3-x)NH3↑+(3-x)H2O (2)
X=0.05 to 0.95 in formula
4) by Li3+3xSb1-xS3 solution is dried and cooling for 60 ° to 100 DEG C in vacuum drying oven or baking oven with protective atmosphere
To room temperature；
5) solid phase agglomerated after cooling is crushed to get product Li is arrived3+3xSb1-xS3。
The stibnite is a kind of antimony mineral of natural output, is the sulfide of trivalent antimony, molecular formula Sb2S3。
The protective atmosphere is the one or several kinds of nitrogen or argon gas.
Antimony base lithium storage materials provided by the invention are suitable as lithium ion cell electrode.With existing li-ion electrode materials
It compares, it has higher charge/discharge capacity, and cost performance is reasonable.
Specific embodiment
Antimony base lithium storage materials provided by the invention are a kind of sulfantimonide of lithium, molecular formula Li3+3xSb1-xS3, Sb in formula
Be positive trivalent, and x is between 0.05 to 0.95 in formula.
[Sb1-xS3](3+x)-It is the derivative of stibnous acid group, wherein three oxygen in stibnous acid group are replaced by sulphur, therefore
Li3+3xSb1-xS3It can regard thioantimonious acid lithium as.From molecular structure angle, and product and raw material from synthesis process
It is seen in inheritance, it is a kind of salt, rather than sulfide；It has the physical property of salt, such as soluble easily in water；And sulfide one
As it is not soluble in water.
As a kind of compound compound, Li3+3xSb1-xS3Electrification during charging (release lithium) and electric discharge (absorbing lithium)
Learning reaction has stage:
(3), (4), (5) three formulas are merged to obtain:
Li3+3xSb1-xS3When being used as lithium ion battery electrode material, its whole metallic element in charge and discharge process,
Electro-chemical activity is all had including Li and Sb, to make it that there is very high charge/discharge capacity.
The step of preparation method of antimony base lithium storage materials, is as follows:
1) broken, ground stibnite powder and ammonium sulfide are mixed by the stoichiometric ratio of (1) formula, then plus are equivalent to
The water of 5 to 10 times of stibnite weight, stirring are dissolved substantially to stibnite；
Sb2S3+3(NH4)2S=2 (NH4)3SbS3 (1)
The stibnite is a kind of antimony mineral of natural output, is the sulfide of trivalent antimony, molecular formula Sb2S3.Stibnite
It is derived from natural crystal, wherein Sb2S3Content be generally only a rough range, when practical operation, should make stibnite excessive, molten
Solving remaining stibnite can continue to use in next molten mine.(the NH obtained after molten mine4)3SbS3Actual weight can basis
The ammonium sulfide of consumption is calculated.
Commercially available ammonium sulfide is usually the aqueous solution of sulfur-bearing about 8% (Containing Sulfur ammonium about 17%), needs to be calculated according to (1) formula
Usage amount.(the NH obtained after molten mine4)3SbS3Solution is unstable, and contacting with air has the tendency that being oxidized.It should be as early as possible after molten mine
Carry out the operation of subsequent step.
2) it is centrifuged or is separated by filtration solid-liquid two-phase, obtain (NH4)3SbS3Solution.
There is remaining stibnite in solid phase, impure mineral such as quartz, calcite can be molten again in use next time
Mine, until stibnite is exhausted substantially.
Residue after molten mine, which should be deposited in Tailings Dam, to be focused on.Other metal sulfides or valuable may wherein be contained
The metallic element of value can be sold when content is sufficiently high using the residue after molten mine as by-product, or voluntarily ore dressing.
3) stoichiometric ratio for pressing (2) formula, in (NH4)3SbS3LiOH is added in solution, and stirring is completely dissolved up to LiOH, obtains
To Li3+3xSb1-xS3Solution；
(1-x)(NH4)3SbS3+ (3+3x) LiOH=Li3+3xSb1-xS3+(3-x)NH3↑+(3-x)H2O (2)
X=0.05 to 0.95 in formula
The ammonia of reaction release is irritant to respiratory tract and is harmful to the human body, it should be noted that ventilation prevents ammonia from assembling.It is real
LiOH answers excessive 1% to 3% when border operates.
Due to NH4 +Ion and Li+Ion can form complex compound in solution, and the reaction of (2) formula is needed heated in next step
It could be carried out completely in journey.
4) by Li3+3xSb1-xS3Solution is dried and cooling for 60 ° to 100 DEG C in vacuum drying oven or baking oven with protective atmosphere
To room temperature.
When dry using vacuum drying oven, because the boiling point of water is reduced because of pressure reduction, it is recommended to use lower drying
Temperature, such as 60 DEG C to 90 DEG C.If using protective atmosphere constant pressure and dry, it is proposed that use higher drying temperature, such as 90 DEG C to 100
DEG C, to improve drying efficiency.
The protective atmosphere is the one or several kinds of nitrogen or argon gas.
5) solid phase agglomerated after cooling is crushed to get product Li is arrived3+3xSb1-xS3。
It elaborates below with reference to embodiment to the present invention.
Embodiment 1
1) 1 kilogram of mineral dust containing stibnite 60% is weighed, 10 kilograms of water, 0.41 kilogram of industrial ammonium sulfide (concentration are added
For 17% solution, 0.0697 kilogram of pure ammonium sulfide, 1.023 moles), stirring is dissolved substantially to stibnite；
2) it is centrifuged or is separated by filtration solid-liquid two-phase, obtain (NH4)3SbS3Solution.
3) 2.87 kilograms of LiOH (119.69 moles) are added in solution, stirring is completely dissolved up to LiOH, obtains
Li5.85Sb0.05S3Solution；
4) by Li5.85Sb0.05S3Solution 60 DEG C of drying in vacuum drying oven, are cooled to room temperature；
5) solid phase agglomerated after cooling is crushed, obtains product Li5.85Sb0.05S3。
Embodiment 2
1) 10 kilograms of mineral dust containing stibnite 34% are weighed, add 5 kilograms of water, (concentration is for 2 kilograms of industrial ammonium sulfides
17% solution, 0.34 kilogram of pure ammonium sulfide, 4.99 moles), stirring is dissolved substantially to stibnite；
2) it is centrifuged or is separated by filtration solid-liquid two-phase, obtain (NH4)3SbS3Solution.
3) 0.4 kilogram of LiOH (16.55 moles) is added in solution, stirring is completely dissolved up to LiOH, obtains
Li3.15Sb0.95S3Solution；
4) by Li3.15Sb0.95S3Solution 80 DEG C of drying in vacuum drying oven, are cooled to room temperature；
5) solid phase agglomerated after cooling is crushed, obtains product Li3.15Sb0.95S3。
Embodiment 3
1) 10 kilograms of mineral dust containing stibnite 50% are weighed, 60 kilograms of water, 3.0 kilograms of industrial ammonium sulfide (concentration are added
For 17% solution, 0.51 kilogram of pure ammonium sulfide, 7.485 moles), stirring is dissolved substantially to stibnite；
3) 1.61 kilograms of LiOH (67.365 moles) are added in solution, stirring is completely dissolved up to LiOH, obtains
Li4.5Sb0.5S3Solution；
4) by Li4.5Sb0.5S3Solution 100 DEG C of drying in band nitrogen sweet smell baking oven, are cooled to room temperature；
5) solid phase agglomerated after cooling is crushed, obtains product Li4.5Sb0.5S3。
Li3+3xSb1-xS3Li and Sb in molecular formula all have electro-chemical activity, its theoretical capacity should be close to Li2S
(Li2The theoretical capacity of S is almost ten times of LiFePO4)；Its molecular structure has similar place with sulfantimonite, from this
One angle sees that charge discharge life should be close to the salts lithium storage materials such as lithium titanate, cobalt acid lithium.It has the high capacity of sulfide concurrently
With the long-life of oxysalt, sulfide and oxyacid salt lithium storage materials will be substantially better than in comprehensive performance.Antimony base stores up lithium
Materials synthesis simple process, energy consumption and at low cost have very high cost performance.
Claims (2)
1. a kind of preparation method of antimony base lithium storage materials, the antimony base lithium storage materials are a kind of sulfantimonide of lithium, molecular formula
For Li3+3xSb1-xS3, Sb is positive trivalent in formula, x=0.05 to 0.95；
It is characterized in that its steps is as follows:
1) stibnite powder and ammonium sulfide that will be broken, ground be mixed by the stoichiometric ratio of (1) formula, then plus are equivalent to brightness antimony
The water of 5 to 10 times of mine weight, stirring are dissolved substantially to stibnite；
Sb2S3+3(NH4)2S=2(NH4)3SbS3 (1)
2) it is centrifuged or is separated by filtration solid-liquid two-phase, obtain (NH4)3SbS3Solution；
3) (NH is pressed4)3SbS3: LiOH=(1-x): the stoichiometric ratio of (3+3x), in (NH4)3SbS3LiOH is added in solution, stirs
Mix until LiOH be completely dissolved, obtain Li3+3xSb1-xS3Solution, x=0.05 to 0.95 in formula；
4) by Li3+3xSb1-xS3Solution is dried and cooled to room for 60 ° to 100 °C in vacuum drying oven or baking oven with protective atmosphere
Temperature；
5) solid phase agglomerated after cooling is crushed to get product Li is arrived3+3xSb1-xS3。
2. the preparation method of antimony base lithium storage materials according to claim 1, it is characterised in that the protective atmosphere is nitrogen
The one or several kinds of gas or argon gas.
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| CN1828980A (en) * | 2005-03-02 | 2006-09-06 | 松下电器产业株式会社 | Negative electrode for non-aqueous secondary battery |
| CN101861673A (en) * | 2009-01-21 | 2010-10-13 | 丰田自动车株式会社 | Sulfide solid electrolyte material |
| CN102782915A (en) * | 2011-03-02 | 2012-11-14 | 独立行政法人产业技术综合研究所 | Negative electrode material for lithium rechargeable battery, method of manufacturing thereof, negative electrode for lithium rechargeable battery, and lithium rechargeable battery |
| CN103138002A (en) * | 2013-03-06 | 2013-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel lithium-sulfur battery and preparation method thereof |
| CN103367798A (en) * | 2012-04-02 | 2013-10-23 | 三星精密化学株式会社 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1828980A (en) * | 2005-03-02 | 2006-09-06 | 松下电器产业株式会社 | Negative electrode for non-aqueous secondary battery |
| CN101861673A (en) * | 2009-01-21 | 2010-10-13 | 丰田自动车株式会社 | Sulfide solid electrolyte material |
| CN102782915A (en) * | 2011-03-02 | 2012-11-14 | 独立行政法人产业技术综合研究所 | Negative electrode material for lithium rechargeable battery, method of manufacturing thereof, negative electrode for lithium rechargeable battery, and lithium rechargeable battery |
| CN103367798A (en) * | 2012-04-02 | 2013-10-23 | 三星精密化学株式会社 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery |
| CN103138002A (en) * | 2013-03-06 | 2013-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel lithium-sulfur battery and preparation method thereof |
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